Int. J. Environmental Technology and Management, Vol. 14, Nos.

1/2/3/4, 2011

115

Adsorption of emulsified oil from spent metalworking

fluid using agro-waste of Cajanus cajan
Sandeep Tiwari*
Department of Mechanical Engineering,
Accurate Institute of Management and Technology,
Greater Noida, Uttar Pradesh, India
Email: sandeep_tiwari1970@rediffmail.com
*Corresponding author

Vimal K. Gupta
Department of Civil Engineering,
G.L.N.A.I.T., Mathura, Uttar Pradesh, India
Email: vimalgupta_gupta@yahoo.com

P.C. Pandey
Department of Mechanical and Industrial Engineering,
University of Roorkee, Uttarakhand, India
Email: pcpandey@yahoo.com

H. Singh
Bundelkhand Institute of Engineering and Technology,
Jhansi, Uttar Pradesh, India
Email: singhharvendra51@gmail.com

P.K. Mishra
Department of Chemical Engineering,
I.T.B.H.U. Varanasi, Uttar Pradesh, India
Email: pkm18@rediffmail.com
Abstract: Safe disposal of spent cutting fluids generated by the use of
semi-synthetic fluids as coolant in material processing industries is a serious
problem. The ultra-filtration method is mostly employed for the processing
of spent cutting fluids. This method is costly and difficult to adopt by small
and medium sized industries. In this study, efforts have been made to produce
adsorbent using agro-waste, i.e. stem of Cajanus cajan in unmodified and
modified form for the removal of emulsified oil. Batch adsorption studies
demonstrated that chemically modified adsorbent has significant capacity to
absorb emulsified oil. The parameters investigated in this study included pH,
temperature, contact time, initial oil concentration, adsorbent dosage and particle
size. The data obtained was also analysed using Langmuir isotherm model and
linear plots conforms its applicability. The dimensionless equilibrium parameter,
RL, signified a favourable adsorption of oil. The adsorption process appeared
to follow pseudo second-order kinetics.
Copyright 2011 Inderscience Enterprises Ltd.

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S. Tiwari et al.
Keywords: adsorption; Langmuir isotherms; MWFs; metalworking fluid;
Cajanus cajan; SCF; spent cutting fluid.
Reference to this paper should be made as follows: Tiwari, S., Gupta, V.,
Pandey, P.C., Singh, H. and Mishra, P.K. (2011) Adsorption of emulsified
oil from spent metalworking fluid using agro-waste of Cajanus cajan,
Int. J. Environmental Technology and Management, Vol. 14, Nos. 1/2/3/4,
pp.115131.
Biographical notes: Sandeep Tiwari is a Professor and Head in the Department
of Mechanical Engineering, Accurate Institute of Management and Technology,
Greater Noida, India. He is a Research Fellow registered at Uttar Pradesh
Technical University, Lucknow, India. He received his BTech in Mechanical
Engineering and MTech from Roorkee University (Now IIT, Roorkee),
India. His research interest includes manufacturing processes, environmental
technology, operations research, treatment and disposal techniques. He has
published various papers in different international journals and conferences.
Vimal K. Gupta is an Assistant Professor in the Department of Civil Engineering
in GLNAIT, Mathura, India. He received his BTech in Civil Engineering from
IET, Lucknow, India and MTech from MNIT, Allahabad, India. He has
published five papers in different journals and conferences. His research interest
includes waste treatment, water purification and designing of structures.
P.C. Pandey is working as a Visiting Professor at the IET, Lucknow. He has
worked in various capacities in the Department of Mechanical and Industrial
Engineering at Roorkee University, Roorkee, India. He has also served as
Chairman of Industrial System Engineering and Management Division at AIT,
Bangkok. He received PhD from University of Nottingham (UK) in 1966 and
BSc Engineering (Mechanical) from IT BHU, Varanasi, India in 1957. Over
350 papers are there to his credit published in international and national
journals. His areas of research include production technology, metal machining
and non-conventional machining.
H. Singh is Director of Bundelkhand Institute of Engineering and Technology,
Jhansi, Uttar Pradesh, India. He received PhD from Ram Manohar Lohia
University, Faizabad, Uttar Pradesh, India. He received his BTech in
Mechanical Engineering from IT BHU, Varanasi, India. He has published
50 papers in international and national journals. His areas of research include
production technology, metal machining and industrial engineering.
P.K. Mishra is an Associate Professor in Chemical Engineering Department, IT
BHU, Varanasi, India. He received his PhD from IT BHU, Varanasi, India,
MTech from Roorkee University and BTech in Chemical Engineering from IT
BHU, Varanasi, India. He has published 100 papers in international and
national journals.

Introduction

Industries involved in traditional metal machining produce several types of wastes, which
sometimes are hazardous to the environment. These industries use large quantity of coolants
for cooling the tool and workpiece, to reduce the friction and wear of cutting tools and dyes
and improving the surface quality of workpiece. The coolants also flush away the metallic
chips generated during machining. The coolants normally used in machining operations

Adsorption of emulsified oil

117

can be classified as synthetics, semi-synthetics or straight oils (Cheryana and Rajagopalan,

1998). Synthetic coolants are composed entirely of water-soluble compounds, whereas the
semi-synthetics are usually an emulsion of stabilised oil-in-water. After prolonged usage,
the emulsified coolants lose their cooling ability and need replacement. In many cases,
the Spent Cutting Fluids (SCFs) are discharged into the environment without treatment,
creating major ecological problems (Bennett, 1983; Hill, 1983; Tansel et al., 2001). Safe
disposal of Semi-Synthetic Fluids (SSFs) has been identified as a serious problem. Pretreatment of SCFs prior to their disposal is now mandatory as per the environmental laws.
SSFs are composed of an emulsion of oil in water and are one of the most extensively
used Metalworking Fluids (MWFs). Some idea of the magnitude of the problem related
to coolant disposal can be obtained from the fact that US industries consume about
$48 billion (Narutaki et al., 1997) worth of coolant, which amounts to 100 million gallons
per year. The German metalworking industries consume about 75,000 tonnes of coolant
per year (Klocke and Eisenblatter, 1997), their annual purchase and disposal cost
amounting to 1 billion Deutsche Marks. Similar studies of the Japanese industries have
revealed that the purchase and safe disposal cost of the cutting fluids in Japan amounts to
29 billion worth of Japanese Yen. It has been observed that safe disposal of the SSFs as
per the Japanese environmental laws would increase the component production cost by
717% (Zimmerman et al., 2004).
A wide range of processing methods for oil-based MWFs has been reported
(Burke, 1991; Anderson et al., 2003; Cheng et al., 2005). The traditional methods for
the separation of oil from water-based emulsions before they can be safely discharged
into the environment can be classified as chemical, mechanical and thermal. Complex
chemical compositions, usually considered as trade secrets by MWFs manufacturers,
make the disposal of MWFs increasingly difficult. Almost all techniques used (except
incineration and biologic treatment) do not ultimately solve the problem of safe removal
of MWFs constituents. Oil and water emulsions are usually broken into oil and water
phases, which need further treatment. These methods are not efficient enough, especially
when the oil droplets are dispersed finely and their concentration is very low (Gryta
et al., 2001). Ultrafiltration (UF) is commonly used for de-emulsification and oil removal
from SCFs before disposal. This process is costly because of higher investment cost and
shorter lives of ultrafiltration tubes. This makes the adoption of filtration technique
difficult particularly by small- and medium-sized industries.
The main drawback of the UF is that it requires substantial amount of investment for
the installation of plant, and involves high running cost due to fouling and short life of
ultrafiltration membranes. Membrane fouling may be due to membrane characteristics,
source (feed) water characteristics and hydraulic conditions of the system. Among these,
organic constituents contained in wastewater effluent, designated as Effluent Organic
Matter (EOM), have been found to play an important role in membrane fouling. UF does
not help in reducing the COD of wastewater and hence additional treatment is required to
control the COD (Cheryana and Rajagopalan, 1998; Lin and Lan, 1998; Cakl et al., 2000;
Jeworski and Heinzleet, 2000; Pierre et al., 2000; Benito and Ruzet, 2002; Hu et al.,
2002; Muszyski et al., 2007). The high-cost ultrafiltration method has prompted the
researchers to look for a relatively inexpensive technique.
In chemical treatment, various chemicals are used to destabilise, de-emulsify or
absorb into the oil phase of a metal removal fluid, thereby allowing the water and oil
phases to separate. But some disadvantages, as given below, restrict its applications:

corrosive chemicals are required for use (sulphuric acid, sodium hydroxide);

chemical treatment is very sensitive to changes in emulsifier (surfactant) chemistry;

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S. Tiwari et al.

specialised instruments are required (pH meter);

instruments require frequent calibration (pH meter) and

balancing chemical reactions, at times, can be more an art than a science.

Adsorption techniques have been widely used for the removal of certain class of
pollutants from water, especially those that are not easily biodegradable. During the past
three decades, several physical, chemical and biological de-colourisation methods have
been developed; few, however, have found applications in paper and textile industries
(Ghoreishi and Haghighi, 2003). Amongst the numerous techniques of dye removal,
adsorption is the most preferred technique as it gives best results. It has been used to
remove different types of colouring materials (Derbyshire et al., 2001; Ho and McKay,
2003; Jain et al., 2003). If the adsorption system is designed correctly, it would produce
a high quality of water. Most commercial systems currently use activated carbon as
adsorbent to remove dyes from wastewater. Use of activated carbon adsorption has been
recommended by the US Environmental Protection Agency as one of the best available
control technologies (Derbyshire et al., 2001). However, activated carbon is associated
with several disadvantages such as expensiveness (higher the quality, greater is the cost),
non-selectiveness and ineffectiveness against dispersed and vat dyes (Babel and
Kurniawan, 2003). The regeneration of saturated activated carbon is also expensive, not
straightforward, and results in loss of the adsorbent. Use of activated carbon, therefore,
cannot be justified (Streat et al., 1995) and therefore there exists a need for inexpensive
adsorbent materials.
Due to the problems mentioned above, research interest into the development and use
of alternative adsorbents to replace the expensive activated carbon has been undertaken.
Attention has been focused on the choice of various industrial and agro-wastes as
adsorbents which can remove pollutants from contaminated water at low cost. Cost is
actually an important parameter for comparing the performance of adsorbent materials.
According to Bailey et al. (1999), a sorbent can be considered low cost if it requires little
processing, is abundantly found in nature or is a by-product or waste from another
industry. Certain waste products from industrial and agricultural operations, e.g. natural
materials and biosorbents, represent potentially economical alternative adsorbents. A
number of them have been tested and proposed for dye removal.
Recently, a number of attempts have been reported regarding the development
of cheaper and effective adsorbents. Non-conventional low-cost adsorbents, including
natural materials, biosorbents and waste materials, have been found to be effective.
Adsorbent from industry and agriculture have been experimented by several research
workers. A wide variety of adsorbent carbons have been prepared from agricultural
and wood wastes, such as bagasse (Valix et al., 2004), rice husk (Guo et al., 2003;
Malik, 2003; Mohamed, 2004) and sawdust (Malik, 2003).
Some research on the treatment of oil-based wastewater using adsorption can be
found in Banerjee et al. (2006), Rajakovic et al. (2007), Hussein et al. (2008), Ibrahim
and Ang (2010) and Khan et al. (2004). The removal of emulsified oils through
adsorption phenomena has been gaining grounds because of low-cost applications that
can be made available to small industrial sectors. The removal of toxic waste by another
waste is more appropriate which mitigate the problem in eco-friendly manner. An
efficient, environmentally compatible and cost-effective adsorbent, Cajanus cajan i.e.
arhar stem, a commonly abundantly available in regions of India, was used for the
preparation of adsorbent for the removal of emulsified oil from SCF. It was demonstrated
through batch adsorption study. Adsorbent characteristic of Unmodified C. Cajan (UCC)

Adsorption of emulsified oil

119

and Modified C. Cajan (MCC) were investigated as adsorbent for the processing of SCF.
The applicability of the Langmuir model for both adsorbent was verified through
the adsorptive kinetics and experimental data analysis. Adsorptive parameters such as
adsorption capacity, adsorption intensity and adsorption affinity of both adsorbents were
determined through the different plots of isotherm.

Material and methods

2.1 Adsorbent preparation and its activation

C. cajan stem, collected from the campus of Institute of Technology, BHU, Varanasi,
India, was repeatedly washed with water to remove dust and soluble impurities. The
sample was dried overnight at about 65C. Dried stem was then grounded to fine powder
and then washed again with distilled water until the washing was free of colour. The
dried powder was passed through 177 m sieve and retained part on 100 m sieve finally
stored in a glass container named as UCC.
UCC was further treated with highly concentrated H2SO4 (49% wt) in the proportion
of 1:1 (weight to volume ratio) in a muffle furnace for 24 hour at 150C. The heated
material was washed with distilled water and soaked in 1% sodium bicarbonate solution
overnight to remove residual acid. The sample was dried in an oven at 105C for
24 hours. After that it was grounded and homogenised by passing it through sieve of
177 m and retained part on 100 m sieve named as MCC.

2.2 Adsorbate solution

Hysol G product of M/s Castrol Limited, semi-synthetic oil, was used to prepare microemulsion by mixing with water and mostly used in the range of 35% oil concentration
by M/s Timken India Limited, Tata Nagar, India. SCF generated by the use of Hysol G
in metal machining operations was collected. Samples were prepared in the range of
1.56.0% oil concentration with water to study the effect of initial oil concentration in
batch adsorption process and other set of experiments was carried out at original oil
concentration of SCF, i.e. 3% (24.6 g L1).

2.3 Batch adsorption studies

Batch adsorption was used to investigate the adsorptive parametric effects for the
adsorption of emulsified oil from SCF. The effect of experimental parameters was also
investigated by varying one parameter while keeping the other parameters constant. The
equilibrium time was selected based on the kinetic experiment. To ensure the accuracy,
reliability and reproducibility of the collected data, all the batch experiments were carried
out in duplicate and the mean values of two datasets are presented. When the relative
error exceeded the relative standard deviation by more than 1.0%, the data were
disregarded and other set of experiments was conducted until the relative error fell within
the acceptable range.
Quantity of 50 ml from each samples were taken to conduct experimentation for the
best value of pertinent factors (Chakravarty et al., 2002). Adjustment of pH was carried
out using 0.1 N NaOH and 0.1 N H2SO4. Orbital thermal shaker (B. Braun, Certomart,
UK) was used for the agitation of the system under investigation.

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S. Tiwari et al.

The amount of emulsified oil adsorbed per unit weight of adsorbent at time t was
computed by the following mass balance equation:
Qt =

( C0 Ct ) V

(1)

ms

where Qt is the weight of oil removed from SCF per unit weight of adsorbent in mg g1,
C0 and Ct are the concentration of oil initially and at time t, respectively, in mg L1, V is
the volume of the SCF in litre and ms is the weight of adsorbent (i.e. C. cajan) in g.
Removal of oil, R (%), was calculated using following equation:
R (%) =

( C0 Ct )
C0

100

(2)

Result and discussion

3.1 Effect of operating parameters on adsorption

The pH of the spent MWF is a significant parameter for the removal of emulsified oil by
adsorption. In the present work, adsorption of oil is studied in the initial pH range of
111. The effect of initial pH on oil removal is shown in Figure 1. Oil removal efficiency
for MCC increased, with decreasing initial pH, from 59.0% (pH = 11) to 95.7% at
pH = 3, taking all adsorptive parameters same for all pH. It is because in the range
9.09.5 of alkaline pH, chemical bonding of different composition of MWF are highly
stable. It was observed that as pH decreased from alkaline to acidic then the oil splitting
(oil-water separation) also increased.
Effect of pH on percentage removal of oil on the surface of MMC (experimental
parameters: initial oil concentration 24.6 g L1; temperature 25C; adsorbent dose
20 g L1; agitation speed 150 rpm; equilibrium time 60 min and particle size
100177 m)
100

90

% Oil removal

Figure 1

80

70

60

pH

10

12

Adsorption of emulsified oil

121

It has been observed that oil removal decreases as temperature of system increases for
both adsorbents. It shows negligible variation in oil removal for the temperature range
from 15C to 25C but sudden decrease in oil removal efficiency was observed when the
temperature increased from 25C to 45C. Therefore, 25C temperature was considered
best value for other sets of experiments in batch adsorption process. It is clear that
adsorption capacity of oil decreases with increase in temperature which indicates exothermic
nature of adsorption on these adsorbents (Ho and Mckay, 1998; Manju et al., 1998;
Tiwari et al., 2010).
Contact time for the adsorption of oil was also studied by taking pH = 3, temperature
25C, initial oil concentration 24.6 g L1, adsorbent dose of 20 g L1, agitation speed of
150 rpm and particle size of 100177 m which gives 95.7% oil removal for MCC as
shown in Figure 2. The batch study shows that the adsorption of oil at time of contact, i.e.
20 minutes, gives 78% of oil removal. After that, the percentage removal of oil increases
slowly till 60 minutes and reaches up to 95.7%. A further increase in the contact time has
a negligible effect on the percentage removal. Therefore, the contact time of 60 minutes
could be considered equilibrium time for the adsorption of oil for other sets of
experiments. The mechanism of solute transfer to the solid includes diffusion through the
fluid film around the adsorbent particle and diffusion through the pores to the internal
adsorption sites. Initially, the concentration gradient between the film and the solid
surface is large, and hence the transfer of solute onto the solid surface is faster (Yu et al.,
2003). It takes lesser time to attain percentage removal of oil up to 78% within first 15
minutes. As time increases, inter-particle diffusion becomes predominant. Hence, solute
takes more time to transfer from solid surface to internal adsorption sites through the pores.

% Oil removal

98

2200

96

2000

94

1800

92

1600

90

1400

88

1200

86

1000
% Oil Removal
Adsorption Capacity

84

800

82
80
10000

600

Adsorbent capacity [mg. g-1]

Effects of initial oil concentration on percentage oil removal and its corresponding
adsorption capacity for MMC (experimental parameters: initial oil concentration
12,300 to 49,200 mg L1; pH = 3; temperature 25C; adsorbent dose 20 g L1;
agitation speed 150 rpm and particle size 100177 m)

Figure 2

400
20000

30000

40000

50000

Initial oil concentration [mg. L-1]

Emulsified oil adsorption is significantly influenced by the initial concentration of oil

in spent MWF. The initial oil concentration was varied from 12.3 to 49.2 g L1
while maintaining the adsorbent dosages at 20 g L1. Figure 2 shows effect of initial oil

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S. Tiwari et al.

concentration on percentage removal of oil and adsorption capacity on MCC. The

percentage removal decreases from 95.7% to 81.6% and adsorption capacity increases
from 588.56 to 2007.36 mg g1 when initial oil concentration increases from 12.3 to
49.2 g L1 at equilibrium time 60 minute and adsorption temperature 25C. The
percentage removal of oil decreases with an increase in initial oil concentration. It
may be due to an increase in number of oil molecules for the fixed amount of adsorbent.
The amount of oil adsorbed per unit mass on MCC increases with increase in oil
concentration which may be due to the complete utilisation of adsorption surface and
active sites available which was not possible at low oil concentration (Periasamy and
Namasivayam, 1996; Kumar and Porkodi, 2007).
The effect of adsorbent dosage on the adsorption of oil removal is shown in Figure 3.
Removal of oil increases with an increase in adsorbent dosage. The percentage of oil
removal increases from 92.9% to 96.01% by increasing the adsorbent dose from 8 to
30 g L1. However, the adsorption capacity showed a decreasing trend with increasing
adsorbent dosage. If the adsorbent amount is increased by keeping the oil concentration
constant, the amount of oil adsorbed per unit mass showed a decrease due to availability
of less number of oil molecules per unit mass of the adsorbent. The adsorption capacity
dropped from 2856.67 to 787 mg g1 by increasing the adsorbent dosage from 8 to
30 g L1.The drop in adsorption capacity is basically due to the sites remaining
unsaturated during the adsorption process.
Effects of adsorbent dose on percentage oil removal and its corresponding adsorption
capacity for MMC (experimental parameters: initial oil concentration 12.3 to
49.2 g L1; pH = 3; temperature 25C; agitation speed 150 rpm; equilibrium
time 60 min and particle size 100177 m)
96.5

3000

96.0
2500

% Oil removal

95.5
95.0

2000
% Oil Removal
Adsorption Capacity

94.5

1500

94.0
93.5

1000
93.0
92.5

Adsorbent capacity [ mg. g-1]

Figure 3

500
5

10

15

20

25

30

Adsorbent dose [ g ]

3.2 Adsorption isotherms

The Langmuir adsorption isotherm has been widely used in many adsorption processes.
The basic assumption of Langmuir theory is that adsorption takes place at specific
homogeneous sites within the adsorbent. It is also assumed that once a site is occupied by

Adsorption of emulsified oil

123

adsorbate molecule no further sorption can occur. The driving force is the concentration
in the solution and the bare area available for adsorption. This isotherm is applicable
when the extent of adsorbate coverage is limited to monolayer adsorption. The isotherm
assumes a dynamic equilibrium between the adsorbed phase and the liquid phase.
Langmuir described chemisorption as the formation of an ionic or covalent bond between
adsorbent and adsorbate. The isotherm equation gives the fractional coverage in the form:

qe
bCe
=
qm 1 + bCe

(3)

where the parameter b = ka/kd, where ka and kd are the respective constants for the
adsorption and desorption and qm is the quantity of adsorbate required to form a single
monolayer on unit mass of adsorbent and qe is the amount adsorbed on unit mass of the
adsorbent when the equilibrium concentration is Ce (Aksu, 2001). Equation (3) can be
rearranged to the form:
Ce
1 1
=
+ Ce
qe bqm qm

(4)

This shows that a plot of Ce qe versus Ce should yield a straight line if the Langmuir
equation is obeyed by the adsorption equilibrium. The slope and the intercept of this line
then give the values of qm and b.
A further analysis of Langmuir equation can be made on the basis of a dimensionless
equilibrium parameter, RL (Hall et al., 1966), also known as separation factor which is
given by:
RL =

1
1 + bCe

(5)

This factor, RL, indicates the shape and type of isotherm. The value of RL lies between 0
and 1 for favourable adsorption, while RL > 1 represents unfavourable adsorption, and
RL = 1 represents linear adsorption while the adsorption process is irreversible if RL = 0
(Namasivayam et al., 1994).
The isotherm data have liberalised using the Langmuir equation and shown in Figure 4
and Table 1 for the adsorption of oil on MCC and UCC. The high value of correlation
coefficient for MCC (R2 = 0.9975) and for UCC (R2 = 0.9648) indicated a good
agreement between the parameters and conforms the monolayer adsorption of oil on to
the adsorbent surface. The constant qm presents adsorption capacity, i.e. 2007.36 mg g1
for MCC in the initial pH range of 23. The constant b, i.e. adsorption energy, is equal to
0.7897 ml mg1 (Table 1). The dimensionless parameter, RL, was found between 0.392
and 0.441 (0 < RL < 1) consistence with the requirement for a favourable process.
Table 1

Langmuir constants for C. cajan

Adsorption capacity
qm (mg g1)

Affinity parameter
b (ml mg1)

Equilibrium
parameter (RL)

Coefficient of
correlation (R2)

Untreated

1721.129

0.000072

0.392

0.9648

Treated

2007.36

0.7897

0.441

0.9975

Cajanus cajan

Notes:

Experimental parameters: adsorbent dose 20 g L1, agitation speed 150 rpm,

adsorbent grain size 100 m, temperature 25C and pH = 3.

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S. Tiwari et al.

Figure 4

Experimentally observed oil removal and predicted isotherms by Langmuir Model for
UCC and MCC (experimental parameters: initial oil concentration 12.3 to 49.2 g L1;
adsorbent dose 20 g L1; pH = 3; temperature 25C; agitation speed 150 rpm and
particle size 100177 m)
2500

q [ mg. g-1]
e

2000

1500

1000
Predicted Langmuir Model for MCC
Predicted Langmuir Model for UCC
Observed Removal for MCC
Observed Removal for UCC

500

0
0

10000

20000

30000

40000

50000

60000

70000

Ce [ mg. L-1]

3.3 Adsorption kinetics

Several kinetic models are in use to explain the mechanism of the adsorption processes.
A simple pseudo-first-order equation due to Lagergren was used by Ho and Mckay
(1998, 1999):
dqt
= kad ( qe qt )
dt

(6)

where qe and qt are the amount of adsorption at equilibrium and at time t, respectively,
and kad is the rate constant of the pseudo-first-order adsorption process. The integrated
rate law after application of the initial condition of qt = 0 at t = 0 becomes:
log ( qe qt ) = log qe kad t 2.303

(7)

Plot of log ( qe qt ) versus t gives a straight line for first-order adsorption kinetics, which
allows computation of the adsorption rate constant, kad. Linear plot between log ( qe qt )
and t is shown in Figures 5 and 6. The kad and qe values at different initial concentrations
of 12.3 g L1 are found to be 1.2782 103 min1 and 686.594 mg g1. The true value of
qe obtained from experiments is 553.71 mg g1. Comparison between obtained and true
value of qe shows that the pseudo-first-order kinetics is inadequate to give a good account
of the kinetics of oil adsorption on chemically modified adsorbent of C. cajan.

Adsorption of emulsified oil

125

Equation (6) differs from a true first-order equation in two ways: (a) the parameter
does not represent the number of available sites and (b) the parameter log qe is an
adjustable parameter and often it is found to be not equal to the intercept of the plot of
log ( qe qt ) versus t, whereas in a true first-order log qe should be equal to the intercept.
In such cases, applicability of the second-order kinetics has to be tested with the rate
equation (Sharma and Bhattacharyya, 2004; Ozturk and Kavak, 2005):
dqt
2
= k 2 ( qe qt )
dt

(8)

where k2 is the second-order rate constant in g mg1 ml1. From the first boundary
conditions, t = 0 to t and qt = 0 to qt, the integrated form of the equation becomes:
1
1
= + k2
q

q
q
( e t) e

(9)

This can be written in the linear form:

t
1 1
= + t
qt h qe

(10)

where h = k2 qe2 can be regarded as the initial sorption rate at t 0 . The plot of t/qt
versus t should give a linear relationship, which allows computation of qe, k and h.
Application of second-order kinetics by plotting t/qt versus t yielded better results as
shown in Figure 7 which represents good agreement between experimental (qe = 553.71)
values and those obtained from the slope (qe = 563.91) of the second-order plots. The
second-order rate constant is found to be 0.00045 g mg1 min1.
Pseudo-first-order plot for the adsorption of oil (experimental parameters: UCC, initial
oil concentration 24.6 g L1; pH = 3; temperature 25C; adsorbent dose 20 g L1;
agitation speed 150 rpm and particle size 100177 m)

Figure 5

ln (Qe - Qt )

UCC
Linearised Plot

R 2 = 0.9141

-2

20

40

60

Time [min]

80

100

120

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S. Tiwari et al.
Pseudo-first-order plot for the adsorption of oil (experimental parameters: MCC, initial
oil concentration 24.6 g L1; pH = 3; temperature 25C; adsorbent dose 20 g L1;
agitation speed 150 rpm and particle size 100177 m)

Figure 6

ln (Qe - Qt)

MCC
Linearised Plot

R 2 = 0.7831
-2

20

40

60

80

100

120

Time [min]

Pseudo-second-order plot for the adsorption of oil (experimental parameters: MCC and
UCC, initial oil concentration 24.6 g L1; pH = 3; temperature 25C; adsorbent dose
20 g L1; agitation speed 150 rpm and particle size 100177 m)

Figure 7

0.14

M CC

0.12

R 2 = 0.999
UCC

0.10

R 2 = 0.999

t/q

0.08

0.06
MCC
Linearised Plot for TCC
UCC
Linearised Plot for UCC

0.04

0.02
0

20

40

60

Time, [min]

80

100

120

Adsorption of emulsified oil

127

Conclusion

The qualitative and quantitative analysis in the research clearly indicated that adsorbent
prepared from C. cajan (i.e. arhar stem) is useful and cost effective for the removal of
emulsified oil from used MWFs. It is found that, after activation with concentrated
sulphuric acid, increase specific surface area of the adsorbent and development of acid
base surface have significant influence on the oil adsorption. The study reveals that
modified form of agro-waste adsorbents yield better results than unmodified adsorbents.
The adsorption of oil using MCC was found to be maximum (95.7%) at pH 3,
temperature 25C, oil concentration 3% v/v, equilibrium time 60 minutes, adsorbent dose
20 g L1 and particle size of 100177 m. The monolayer mode of adsorption has been
confined as illustrated by Langmuir plots. The monolayer adsorption capacity (Q0)
decreased with increase in temperature, confirming exothermic nature of the SCFs. The
rate of the adsorption is governed by pseudo-second-order rate equation. Carbon users
would also be benefited because this material offers a viable alternative to costly
activated carbons. Future work may deal with the development of online treatment plants
using continuous adsorption process. The experimental work could also be extended to
include other agro-waste materials, e.g. maize stem, wheat husk, etc.
The findings and conclusion of the results duly validated by the outcomes of
experimental data substantiated that use of adsorbents prepared by C. cajan (arhar stem)
shall radically minimised the overall cost in removing emulsified oil from used MWFs.
The research outcomes indicate scope of further research based on the impact of various
factors, dimensions and parameters which may play an instrumental role in minimisation
of overall cost and maximisation of productivity to develop online treatment plant.
Small and medium enterprises in various countries may leverage from the finding and
outcome of this research and optimise the productivity of various resources, ultimately
leading to maximisation of productivity and value of organisation by minimising the cost
and maximising the profit to research global competition and sustainability.

References
Aksu, Z. (2001) Equilibrium and kinetic modeling of cadmium (II) biosorption by C. vulgaris in a
batch system: effect of temperature, Separation and Purification Technology, Vol. 21, No. 3,
pp.285294.
Anderson, J.E., Kim, B.R., Mueller, S.A. and Lofton, T.V. (2003) Composition and analysis of
mineral oils and other organic compounds in metalworking and hydraulic fluids, Critical
Reviews in Environ Science and Technology, Vol. 33, No. 1, pp.73109.
Babel, S. and Kurniawan, T.A. (2003) A Research Study on Chromium Removal from
Electroplating Wastewater using Chemically Treated Zeolite, Thammasat University,
Thailand.
Bailey, S.E., Olin, T.J., Bricka, R.M. and Adrian, D.D. (1999) A review of potentially low costs
sorbents for heavy metals, Water Research, Vol. 33, No. 11, pp.24692479.
Banerjee, S.S., Joshi, M.V. and Jayaram, R.V. (2006) Treatment of oil spills using organo-fly ash,
Desalination, Vol. 195, Nos. 13, pp.3239.
Bennett, E.O. (1983) Water based cutting fluids and human health, Tribology International,
Vol. 16, No. 3, pp.133136.

128

S. Tiwari et al.

Benito, Y. and Ruzet, M.L. (2002) Reverse osmosis applied to metal finishing wastewater,
Desalination, Vol. 142, No. 3, pp.229234.
Burke, J.M. (1991) Waste treatment of metalworking fluids: a comparison of three common
methods, Lubrication Engineering, Vol. 47, No. 4, pp.238246.
Cakl, J., Bauer, I., Dolecek, P. and Mikulsek, P. (2000) Effects of backflushing conditions on
permeate flux in membrane crossflow microfiltration of oil emulsion, Desalination, Vol. 127,
No. 2, pp.189198.
Chakravarty, S., Dureja, V., Bhattacharyya, G., Maity, S. and Bhattacharjee, S. (2002) Removal
of arsenic from groundwater using low cost ferruginous manganese ore, Water Research,
Vol. 36, No. 3, pp.625632.
Cheng, C., Phipps, D. and Alkhaddar, R.M. (2005) Treatment of spent metalworking fluids,
Water Research, Vol. 39, No. 17, pp.40514063.
Cheryana, M. and Rajagopalan, N. (1998) Membrane processing of oily streams wastewater
treatment and waste reduction, Journal of Membrane Science, Vol. 151, No. 1, pp.1328.
Derbyshire, F., Jagtoyen, M., Andrews, R., Rao, A., Martin-Gullon, I. and Grulke, E. (2001)
Carbon materials in environmental applications, in Radovic, L.R. (Ed.): Chemistry and
Physics of Carbon, Vol. 27, Marcel Dekker, New York, pp.166.
Ghoreishi, S.M. and Haghighi, R. (2003) Chemical catalytic reaction and biological oxidation
for treatment of non-biodegradable textile effluent, Chemical Engineering Journal, Vol. 95,
No. 1, pp.163169.
Gryta, M., Karakulski, K. and Morawski, A.W. (2001) Purification of oily wastewater by hybrid
UF/MD, Water Research, Vol. 35, No. 15, pp.36653669.
Guo, Y., Yang, S., Fu, W., Qi, J., Li, R., Wang, Z. and Xu, H. (2003) Adsorption of malachite
green on micro- and mesoporous rice husk-based active carbon, Dyes and Pigments, Vol. 56,
No. 3, pp.219229.
Hall, K.R., Eagleton, L.C., Acrivos, A. and Vermeulen, T. (1966) Pore and solid diffusion
kinetics in fixed bed adsorption under constant pattern conditions, Industrial & Engineering
Chemistry Fundamentals, Vol. 5, No. 2, pp.212219.
Hill, E.C. (1983) Microbial aspects of health hazards from water based metal working fluids,
Tribology International, Vol. 16, No. 3, pp.136140.
Ho, Y.S. and McKay, G. (2003) Sorption of dyes and copper ions onto biosorbents, Process
Biochemistry, Vol. 38, No. 7, pp.10471061.
Ho, Y.S. and Mckay, G. (1998) A comparison of chemisorption kinetic models applied to
pollutants removal on various sorbents, Process Safety and Environmental Protection,
Vol. 76, No. 4, pp.332340.
Ho, Y.S. and Mckay, G. (1999) Comparative sorption kinetic studies of dyes and aromatic
compounds on to fly ash, Journal of Environmental Science and Health, Part A, Vol. 34,
No. 5, pp.11791204.
Hu, X., Bekassy-Molnar, E. and Vatai, G. (2002) Study of ultrafiltration behavior of emulsified
metalworking fluids, Desalination, Vol. 149, pp.191197.
Hussein, M., Amer, A.A. and Sawsan, I.I. (2008) Oil spill sorption using carbonized pith bagasse:
trial for practical application, International Journal of Environment Science and Technology,
Vol. 5, No. 2, pp.233242.
Ibrahim, W.S. and Ang, M. (2010) Removal of emulsified oil from oily wastewater using
agricultural waste barley straw, Biochemical Engineering Journal, Vol. 49, No. 1, pp.7883.
Jain, A.K., Gupta, V.K., Bhatnagar, A. and Suhas (2003) Utilization of industrial waste products
as adsorbents for the removal of dyes, Journal of Hazardous Materials, Vol. 101, No. 1,
pp.3142.
Jeworski, M. and Heinzleet, E. (2000) Combined chemical-biological treatment of wastewater
containing refractory pollutants, Biotechnology Annual Review, Vol. 6, pp.163196.

Adsorption of emulsified oil

129

Khan, F.I., Husain, T. and Hejazi, R. (2004) An overview and analysis of site remediation
technologies, Journal of Environmental Management, Vol. 71, No. 2, pp.95122.
Klocke, F. and Eisenblatter, G. (1997) Dry cutting, Annals of the CIRP, Vol. 46, No. 2,
pp.519526.
Kumar, K.V. and Porkodi, K. (2007) Batch adsorber design for different solution
volume/adsorbent mass ratios using the experimental equilibrium data with fixed solution
volume/adsorbent mass ratio of malachite green onto orange peel, Dyes and Pigments,
Vol. 74, No. 3, pp.590594.
Lin, S.H. and Lan, W.J. (1998) Performance characteristics of waste oil emulsion treatment
by ultrafiltration, Journal of Environmental Science and Health, Part A, Vol. 33, No. 3,
pp.385404.
Malik, P.K. (2003) Use of activated carbons prepared from sawdust and rice-husk for adsorption
of acid dyes a case study of Acid Yellow 36, Dyes and Pigments, Vol. 56, No. 3,
pp.239249.
Manju, G.N., Raji, C. and Anirudhan, T.S. (1998) Evaluation of coconut husk carbon for removal
of arsenic from water, Water Research, Vol. 32, pp.30623070.
Mohamed, M.M. (2004) Acid dye removal: comparison of surfactant-modified mesoporous
FSM-16 with activated carbon derived from rice husk, Journal of Colloid and Interface
Science, Vol. 272, No. 1, pp.2834.
Muszyski, A., Zaleska-Radziwill, M., Lebkowska, M. and Nowak, D. (2007) Biological and
electrochemical treatment of used metalworking fluids: a toxicity-reduction evaluation,
Archives of Environmental Contamination and Toxicology, Vol. 52, No. 4, pp.483488.
Namasivayam, C., Jaikumar, R. and Yamuna, R.T. (1994) Dye removal from wastewater by
adsorption on Fe(III)/Cr(III) hydroxide, Waste Management, Vol. 14, No. 7, pp.643650.
Narutaki, N., Yamane, Y., Tashima, S. and Kuroki, H. (1997) A new advanced ceramic for dry
machine, Annals of the CIRP, Vol. 16, No. 1, pp.4348.
Ozturk, N. and Kavak, D. (2005) Adsorption of boron from aqueous solutions using fly ash: batch
and column studies, Journal of Hazardous Materials, Vol. 127, Nos. 13, pp.8188.
Periasamy, K. and Namasivayam, C. (1996) Removal of copper (II) by adsorption onto peanut
hull carbon from water and copper plating industry wastewater, Chemosphere, Vol. 32,
No. 4, pp.769789.
Pierre, C., Gavarri, J.R., Musso, J., Durand, J. and Tabaries, F. (2000) Relation between chemical
treatments and defect structure of calcium carbonates in industrial ashes, Waste Management,
Vol. 20, No. 4, pp.299309.
Rajakovic, V., Aleksic, G., Radetic, M. and Rajakovic, L.J. (2007) Efficiency of oil removal from
real wastewater with different sorbent materials, Journal of Hazardous Materials, Vol. 143,
Nos. 12, pp.494499.
Sharma, A. and Bhattacharyya, K.G. (2004) Adsorption of chromium (VI) on Azadirachta Indica
(neem) leaf powder, Adsorption, Vol. 10, No. 4, pp.327338.
Streat, M., Patrick, J.W., Camporro, M. and Perez, J. (1995) Sorption of phenol and parachlorophenol from water using conventional and novel activated carbons, Water Research,
Vol. 29, No. 2, pp.467472.
Tansel, B., Regula, J. and Shalewitz, R. (2001) Evaluation of ultra-filtration process performance
for treatment of petroleum contaminated waters, Journal of Water, Air, & Soil Pollution,
Vol. 126, Nos. 34, pp.291305.
Tiwari, S., Pandey, P.C., Singh, H. and Mishra, P.K. (2010) A comparative study of the
performance behavior of adsorbent materials used for the treatment of Spent Cutting Fluids,
International Journal of Environmental Technology and Management, Vol. 13, No. 2,
pp.206220.

130

S. Tiwari et al.

Valix, M., Cheung, W.H. and McKay, G. (2004) Preparation of activated carbon using low
temperature carbonisation and physical activation of high ash raw bagasse for acid dye
adsorption, Chemosphere, Vol. 56, No. 5, pp.493501.
Yu, L.J., Shukla, S.S., Doris, K.L., Shukla, A. and Margrave, J.L. (2003) Adsorption of chromium
from aqueous solutions by maple sawdust, Journal of Hazardous Materials, Vol. 100,
Nos.13, pp.5363.
Zimmerman, J.B., Hayes, K.F. and Skerlos, S.J. (2004) Influence of ion accumulation on the
emulsion stability and performance of semi-synthetic metalworking fluids, Environmental
Science & Technology, Vol. 38, No. 8, pp.24822490.

Adsorption of emulsified oil

Symbols
C0

Initial oil concentration (mg L1)

Ct

Concentration of oil at time t (mg L1)

qm Adsorption capacity (mg gm1)

ka

Adsorption constant

kd

Desorption constant

kad Rate constant of the pseudo-first-order adsorption process

b

Langmuir constant

ms

weight of adsorbent (gm)

qe

Oil removed per unit weight of adsorbent (mg gm1)

qt

Adsorbed oil per unit weight of adsorbent at time t (mg gm1)

RL

Separation factor

volume of the SCF (litre)

Abbreviations
MWFs

Metalworking Fluids

SCFs

Spent Cutting Fluids

UCC

Unmodified C. Cajan

MCC

Modified C. Cajan

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